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研究生:鄭至翔
研究生(外文):Chih-Hsiang Cheng
論文名稱:電化學氧化法應用於異丁烷/烯烴烷化製程廢酸中有機物去除之研究
論文名稱(外文):Removal of organic compounds in spent acid from isobutene/olefinalkylation process by electrochemical oxidation
指導教授:陳文星陳文星引用關係
指導教授(外文):Wen-shing chen
學位類別:碩士
校院名稱:國立雲林科技大學
系所名稱:化學工程與材料工程研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2009
畢業學年度:97
語文別:中文
論文頁數:77
中文關鍵詞:電化學氧化法廢酸異丁烷/烯烴電芬頓氧化法
外文關鍵詞:hydroxyl freeradicalsbutyleneElectro-Fentonisobutene/olefin alkylation process
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本研究係應用電化學氧化法處理異丁烷/烯烴之烷化製程衍生廢酸,藉由丁烯通入高濃度硫酸中,以模擬烷化製程所產生的廢酸,其有機物濃度約為10970~23770mg/L。本文中將探討影響有機物去除之操作變數效應,包括施予電壓、反應溫度、硫酸濃度及氧氣流量。實驗測試結果顯示電解電壓為5volt、反應溫度為298 K、硫酸濃度為96 wt%及通氧量120ml/min 的操作條件下,歷經12 小時之電解反應,有機物去除效率可達58%,而有機物之氧化降解主要是利用陰極還原氧氣所生成之過氧化氫,氧氣之主要來源殆為陽極上水份之電解。另一方面本研究嘗試利用電芬頓氧化法處理異丁烷/烯烴之烷化製程廢酸,惟處理效果並不理想,有機物去除率僅為,其原因殆為部份亞鐵離子於陰極上還原為金屬鐵,因而遮蔽部份鉑極板,使得氧氣還原為過氧化氫之產率降低。
In this study the electrochemical oxidation method is employed todispose the spent acid from isobutene/olefin alkylation process. The spentacid produced in the laboratory is by means of passing a butene streamthrough concentrated sulfuric acid, of which organic compoundsconcentration is 10970-23770 mg/L. Effects of operating parameters onthe performance of removal of organic compounds in spent acid havebeen investigated, including electrode potential, reaction temperature,sulfuric acid concentration and oxygen dosage. The removal percentageof TOC reaches 58% under the conditions of electrode potential = 5V, T =298 K, O2 = 120 ml/min and H2SO4 = 96 wt% after the duration of 12 hrs.The phenomenon observed is attributed to the oxidizing agentelectrogenerated in the cathode, wherein the oxygen is reduced intohydrogen peroxide. The oxygen gas is believed to mainly derive fromwater electrolysis in the anode. In another respect, the degradation oforganic compounds in spent acid using Electro-Fenton method has alsobeen conducted. The removal percentage of organic compounds is merely%. The observation may be explained by the reduction of ferrous iron inthe cathode, which would block some active sites for electrogeneration ofhydrogen peroxide.
目 錄中文摘要 ----------------------------------------------------------------------------- i英文摘要 ----------------------------------------------------------------------------- iii致謝 ----------------------------------------------------------------------------- v目錄 ----------------------------------------------------------------------------- vi圖目錄 ----------------------------------------------------------------------------- ix表目錄 ----------------------------------------------------------------------------- xi一、 前言1-1 研究緣起--------------------------------------------------------------- 11-2 研究目的與內容---------------------------------------------------- 2二、 背景資料與文獻2-1 烷化石油--------------------------------------------------------------- 42-2 烷化反應介紹-------------------------------------------------------- 42-2-1 熱烷化法--------------------------------------------------------------- 42-2-1 觸媒烷化法----------------------------------------------------------- 52-3 廢硫酸再生技術---------------------------------------------------- 72-4 電解氧化原理-------------------------------------------------------- 82-4-1 直接氧化--------------------------------------------------------------- 192-4-2 間接氧化--------------------------------------------------------------- 20vii2-5 高級氧化程序-------------------------------------------------------- 21三、 研究方法3-1 實驗材料--------------------------------------------------------------- 253-2 實驗藥品--------------------------------------------------------------- 273-3 實驗分析儀器-------------------------------------------------------- 303-4 實驗裝置--------------------------------------------------------------- 323-5 電解反應系統-------------------------------------------------------- 333-6 實驗流程--------------------------------------------------------------- 343-7 實驗分析原理-------------------------------------------------------- 353-7-1 總有機碳含量(TOC)----------------------------------------------- 353-7-2 過氧化氫濃度測定------------------------------------------------- 353-7-3 Fe3+鐵離子濃度測定----------------------------------------------- 363-7-4 氣相層析質譜儀(GC/MS)---------------------------------------- 373-7-5 Karl- Fischer 水份檢測----------------------------------------- 39四、 結果與討論----------------------------------------------------------- 414-1 實驗前處理----------------------------------------------------------- 414-2 間接電解氧化法---------------------------------------------------- 414-3 廢酸電解中間物之鑑定------------------------------------------ 514-4 電芬頓氧化法-------------------------------------------------------- 56viii五、 結論---------------------------------------------------------------------- 59參考文獻 ----------------------------------------------------------------------------- 61
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